J. Min. Metall. Sect. B-Metall. 52 (1) B (2016) 17 - 24
Jo u rn al o f Min in g an d Met allu rgy,
S ect ion B: Met a llu rg y
PHOSPHATE VALORIZATION BY DRY CHLORINATION ROUTE
N. Kanari,a*, N. Menadb, F. Diota, E. Allaina, J. Yvona
Université de Lorraine, UMR 7359 CNRS, CREGU, GeoRessources Laboratory, Vandoeuvre-les-Nancy, France
b
BRGM, Orléans, France
a
Abstract
(Received 04 March 2015; accepted 24 September 2015)
This work deals with the extraction of phosphorus chlorinated compounds from phosphate materials using chlorination with
gaseous chlorine. An industrial sample of dicalcium phosphate dihydrate, after transformation into calcium pyrophosphate
(Ca2P2O7), is subjected to reactions with Cl2+CO+N2 and Cl2+C+N2 at temperatures ranging from 625 to 950 °C using
boat experiments. Gathering results of the thermodynamic predictions and TG/DT analysis with those of SEM and XRD
examinations of the chlorinated residues allowed the interpretation of phenomena and reactions mechanism occurring
during the calcium pyrophosphate carbochlorination.
Reaction rate of Ca2P2O7 by Cl2+CO+N2 at 950 °C is slowed down due to the formation of a CaCl2 liquid layer acting as
a barrier for the diffusion of the reactive gases and further reaction progress. While, the carbochlorination with Cl2+C+N2
led to almost full chlorination of Ca2P2O7 at 750 °C and the process proceeds with an apparent activation energy of about
104 kJ/mol between 625 and 750 °C.
Carbochlorination technique can be considered as an alternative and selective route for the valorization of low grade
phosphates and for the phosphorus extraction from its bearing materials.
Keywords: Dicalcium phosphate dihydrate; Calcium pyrophosphate; Chlorination; Valorization
1. Introduction
Phosphorus, based in a vast variety of the
phosphorus minerals, especially phosphates, is vital
for flora, fauna and human life. Most of phosphate
bearing materials are used in the agriculture as
fertilizer and another important end use of phosphates
is detergency. Further, it seems that there are no
consistent substitutes for phosphorus in agriculture.
According to available statistic data [1], the world
production of phosphate rock (26-34 % P2O5) has
more than tripled during the last fifty years reaching
217 million tons by 2012. With this increase
production rate and by taking into account that the
phosphate natural resources are limited, the depletion
of the economically viable phosphorus reserves is
evident within a near future. One way to overcome
this difficulty should be the exploitation and
upgrading of low grade phosphate ores and recycling
of the phosphorus constituents contained in the
wasted materials. A coherent overview of the
techniques (physical and thermal routes) used for
producing high-grade phosphate products suitable for
fertilizers and other phosphate compounds is given
elsewhere [2].
Thermal route is also used for the reduction of
* Corresponding author: [email protected]
DOI:10.2298/JMMB150304027K
phosphates by carbon in presence of SiO2 at
temperatures, often, as high as 1600 °C. The
elemental phosphorus is produced followed by its
subsequent oxidation to phosphorus pentoxide which
is an important precursor for the H3PO4 synthesis. The
research works related to the action of gaseous
chlorine on the phosphates are not found in the
literature or they are based on old studies. Recent few
works are focused on the behaviors of phosphorus
compounds during removal of heavy metals contained
in the sewage sludge ash using thermochemical
methods, especially, chlorination [3-5]. However, a
good number of investigations are devoted to the
chlorination technique for the separation and
extraction of valuable metals from raw and residual
materials [6-13]. Other reports concerned the
reactivity and kinetics of interaction of chlorine with
several rare earth elements oxides such as CeO2 [14],
Sm2O3 [15], Y2O3 [16], Nd2O3 [17] and La2O3 [18].
In this context, this study is devoted to the
possibility of the phosphate valorization and
extraction of phosphorus chlorinated compounds by
dry chlorination route. As the first step of the
investigation, the results presented here are almost
related to the reaction of dicalcium phosphate
dihydrate (CaHPO4.2H2O) with Cl2+CO+N2 and
18
N. Kanari et al. / JMM 52 (1) B (2016) 17 - 24
Cl2+C+N2 under isothermal conditions. Both
thermodynamic and kinetics aspects of the
carbochlorination reactions are discussed in order to
achieve a selective separation process of the
phosphate constituents. This work is an extension of
our most important findings concerning the
chlorination processes summarized earlier [19], as
well as of some kinetics of the chlorination reactions
of various oxides in presence of reducing and /or
oxidizing atmosphere [20-24].
2. Materials and experimental procedures
A wet sample of dicalcium phosphate dihydrate
(CaHPO4.2H2O), known also as brushite, of industrial
origin, is used for this study. CaHPO4.2H2O represents
about 98.0 % of dried solid of the sample. Raw wet
sample is heated at 150 °C and X-ray diffraction
(XRD) analysis revealed the presence of
CaHPO4.2H2O and neo-formed monetite (CaHPO4) as
main crystallized phases. This sample is mostly used
for the carbochlorination tests and it is designated as
DCPI. Both samples (wet and dried samples) are
subjected to the thermogravimetric (TG) analysis
under N2 atmosphere over 20-1000 °C temperature
range with a linear heating rate of 5 °C/min. Results
are depicted in Fig. 1 as evolution of the percent mass
loss (% ML) as a function of the temperature. Solid
products obtained at 200 °C, 600°C and 1000°C are
examined by XRD. The % ML observed for the wet
sample at temperatures lower than 100 °C
corresponds to the free water removing of the wet
brushite sample. Transformation of brushite into
monetite occurred between 100 °C and 200 °C, as
confirmed by XRD. The next step of % ML observed
at T > 400 °C is attributed to the thermal conversion
of the monetite into calcium pyrophosphate (Ca2P2O7)
which is stable up to at least 1000 °C.
Charcoal is chosen as carbon bearing substance
for the carbochlorination of DCPI. XRD analysis
showed two broad diffraction peaks attributed to
slightly graphitized carbon structure. Used gases (N2,
CO and Cl2) are of a high purity (99.9 wt %). Boat
chlorination experimental tests were performed in a
horizontal setup described previously [22]. This setup
is composed of a gas measuring unit followed by a gas
purification item and a horizontal electric furnace.
The chlorination residues were examined by scanning
electron microscopy-energy dispersive spectroscopy
(SEM-EDS) and XRD.
3. Results and discussion
3.1. Thermodynamic elements
As noted in the previous section, thermal
treatment of CaHPO4.2H2O and CaHPO4 under
nitrogen atmosphere at temperatures higher than
500°C led to the formation of the calcium
pyrophosphate (Ca2P2O5). Therefore, Ca2P2O5 is
considered as only compound for the thermodynamic
calculations
of
chlorination
(Cl2)
and
carbochlorination (Cl2+CO; Cl2+C) reactions. The
evolution of free standard energy changes (G°) as a
function of the temperature for the overall reactions of
Ca2P2O7 with Cl2, Cl2+CO and Cl2+C (Eq.1 through 9)
are calculated by using thermochemical databases
[25-26] and the obtained results are traced in Fig. 2.
1 / 5 Ca2 P2O7 + Cl2 =
(1)
1 / 5 Ca2 P2O7 + Cl2 =
(2)
1 / 7 Ca2 P2O7 + Cl2 =
(3)
1 / 5 Ca2 P2O7 + Cl2 + 7 / 5 CO =
(4)
1 / 5 Ca2 P2O7 + Cl2 + CO =
(5)
1 / 7 Ca2 P2O7 + Cl2 + CO =
(6)
1 / 5 Ca2 P2O7 + Cl2 + 7 / 10 C =
(7)
1 / 5 Ca2 P2O7 + Cl2 + 1 / 2 C =
(8)
1 / 7 Ca2 P2O7 + Cl2 + 1 / 2 C =
(9)
2 / 5 CaCl2 + 2 / 5 PCl3 + 7 / 10 O2
2 / 5 CaCl2 + 2 / 5 POCl3 + 1 / 2 O2
2 / 7 CaCl2 + 2 / 7 PCl5 + 1 / 2 O2
2 / 5 CaCl2 + 2 / 5 PCl3 + 7 / 5 CO2
2 / 5 CaCl2 + 2 / 5 POCl3 + CO2
2 / 7 CaCl2 + 2 / 7 PCl5 + CO2
2 / 5 CaCl2 + 2 / 5 PCl3 + 7 / 10 CO2
2 / 5 CaCl2 + 2 / 5 POCl3 + 1 / 2 CO2
2 / 7 CaCl2 + 2 / 7 PCl5 + 1 / 2 CO2
Figure 1. Behavior of the brushite samples (wet and dried
sample) under nitrogen atmosphere heated up to
1000°C
Chlorination of Ca2P2O5 by chlorine in absence of
reducing atmosphere seems to be not feasible since
the value of G° are higher than 100 kJ/mol Cl2 in
whole temperature interval studied and whichever is
the phosphorus chlorinated species (Fig. 2a).
N. Kanari et al. / JMM 52 (1) B (2016) 17 - 24
19
Carbochlorination reactions of the calcium
pyrophosphate with Cl2+CO and Cl2+C (Fig. 2b and
2c, respectively) are characterized by negative values
of the (G°) resulting to a favorable process from
thermodynamic point of view.
The phase predominance area diagrams (Fig. 3)
for the system Ca-O-Cl and P-O-Cl as a function of
temperature and partial pressure of chlorine at two
fixed partial pressures of oxygen (pO2) are established
by using HSC Chemistry thermochemical database
[26].
Figure 2. Standard free energy change of the
chlorination reactions of the Ca2P2O7
with: (a): Cl2; (b): Cl2+CO; (c): Cl2+C
Figure 3. Evolution of the phase stability area as a
function of the temperature of: (a): Ca-O-Cl
for pO2 = 10.13 kPa; (b): Ca-O-Cl for
pO2 = 1.013 x 10-18 kPa; (c): P-O-Cl for
pO2 = 1.013 x 10-18 kPa
20
N. Kanari et al. / JMM 52 (1) B (2016) 17 - 24
Calcium chloride is the predominant phase in CaO-Cl system at high partial pressure of chlorine at two
chosen values of pO2 (Fig. 3a and 3b). As could be
expected, its predominance area is extended at low
oxygen potential (pO2 = 1.013x10-18 kPa). Phosphorus
pentoxide (with molecular formula P4O10) is the only
stable phase in the P-O-Cl system for pO2 = 10.13 kPa
at whole temperature range studied (it is not shown in
the Fig. 3). However, phosphorus oxychloride
(POCl3) and trichloride (PCl3) are the most stable
phases for temperatures higher than 300 °C and 600 °C,
respectively for low oxygen potential (pO2 = 1.013x
10-18 kPa) and for high partial pressure of chlorine
(Fig. 3c). Decreasing the oxygen partial pressure at
values lower than (pO2 = 1.013x10-18 kPa) leads to the
formation of phosphorus trichloride as the main phase
in equilibrium with P4O10. In summary, these
thermodynamic data indicate that Ca2P2O7 can be
chlorinated by chlorine only in presence of a reducing
agent leading to the formation of the phosphorus
chlorinated compounds.
Another interesting thermodynamic knowledge of
the above mentioned systems is the vapor pressure of
the synthetized chlorides. Fig. 4 gives the vapor
pressure of phosphorus, iron and calcium chlorides as
a function of reciprocal temperature. It is clear from
this figure that the large difference between the vapor
pressure of phosphorus chlorides (PCl3, POCl3, PCl5)
and that of CaCl2 will allow their separation.
Similarly, these phosphorus chlorides can also be
separated from iron chloride by fractional distillation
and/or by controlled cooling of the gas phase.
Oxidation of these phosphorus chlorides leads to the
synthesis of phosphorus pentoxide.
This thermodynamic study summarizes the basic
elements for a selective extraction the phosphorus
chlorinated compounds from calcium phosphate
during its chlorination, while the kinetics parameters
of the process will be revealed through the
experimental results described in the following
sections.
Figure 4. Evolution of the vapor pressure as a function of
temperature for several chlorides generated
during phosphate chlorination
3.2. Carbochlorination with Cl2+CO+N2
The first carbochlorination tests of the DCPI were
performed at 950°C on about 3 grams of sample,
when the reaction time was varied from 0.5 to 4.0
hours. A gaseous Cl2+CO+N2 mixture with a total gas
flow rate of 100 L/h containing 30 % Cl2+CO and
having a Cl2/CO molar ratio equal to 1 is used for the
experimental tests. This high gas flow rate aims at
avoiding reactive gas starvation and minimizing the
mass transfer phenomena. Results are represented in
Fig. 5a as an evolution of the sample % ML versus
reaction time. A rough examination of these data
Figure 5. Evolution of the % mass loss of the sample as a
function of time during carbochlorination of
DCPI at 950 °C (a) and SEM-EDS analysis
results (b)
N. Kanari et al. / JMM 52 (1) B (2016) 17 - 24
indicates that % ML increased almost linearly with the
reaction time. Such % ML curve shapes recall a gassolid process with an overall rate governed by the
reaction rate occurring at infinite slabs and/or the
process controlled by the volatilization rate of liquid
reaction products.
SEM-EDS spectra of the DCPI initial sample and
that of the carbochlorination residue obtained after 4
hours are showed in Fig. 5b. These spectra are almost
identical except the presence of chlorine in the
chlorination residue which is attributed to CaCl2. Note
that all phosphorus chlorinated compounds are highly
volatile at 950 °C (see Fig. 4). This result suggests
that the presence of the liquid calcium chloride affects
the chlorination process. It probably covers the DCPI
particles acting thus as a barrier for the diffusion of
the reactive (Cl2+CO) gas to the reaction zone. The
progress of reaction then depends on the volatilization
rate of liquid CaCl2.
To have an idea about the thermal behavior of the
calcium chloride, a TG analysis coupled with
differential thermal (DT) measurement is performed
under nitrogen and the obtained results are shown in
Fig. 6.
21
chloride. For these reasons it was suggested to
achieve the chlorination of DCPI at temperatures
lower than the melting point of CaCl2. Further, the
solid carbon is used as reducing agent instead of
gaseous carbon monoxide which can disperse the
solid CaCl2 product creating free paths for the
chlorine diffusion.
3.3. Carbochlorination with Cl2+C+N2
Mixtures of DCPI and carbon with various
C/DCPI molar ratios were prepared. The most
appropriate mixture for the carbochlorination tests is
chosen to be (DCPI+C) having 1.5 times more carbon
than the stoichiometric amount required according to
Eq. (7). A gaseous Cl2+N2 mixture with a total flow
rate of 100 L/h containing 30 % Cl2 is used for the
chlorination. Experimental tests were carried out
under isothermal conditions in the range 625 - 900 °C
for a reaction time of 8 h. Results are plotted in Fig. 7
as evolution of % ML of the DCPI+carbon sample vs
temperature.
Figure 7. Evolution of the % mass loss of the sample as a
function of the temperature during
carbochlorination of DCPI by C+Cl2+N2
for 8 hours
Figure 6. Results of the TG-DT analysis for the calcium
chloride in nitrogen atmosphere
Data recorded above 750°C are the most important
for this study. The endothermic peak at 784°C is
attributed to the melting of CaCl2 and it is close to the
fusion point (775°C) of the calcium chloride found in
the literature [26]. Then, the mass loss recorded
beyond this temperature is due to the volatilization of
the liquid calcium chloride. A comparison of these
results with the previous ones, indicates that the
carbochlorination rate of the calcium phosphate is
affected by the physical properties, i.e. melting point
and volatilization rate, of the synthetized calcium
As seen in Fig. 7, a regular and almost exponential
function shape of %ML of the sample vs temperature
is recorded for the treatment temperature up to
750°C. Afterward, the reaction extent decreased and
temperatures as high as 900°C are necessary to have
the similar %ML as that obtained at 750°C. Again, the
complications of the DCPI carbochlorination at high
temperatures are interpreted assuming that the process
is affected by fusion of CaCl2. Similar phenomena
have been reported previously for the
carbochlorination of MgO [22].
Attempts were made to follow the evolution of the
elemental and mineralogical composition of the
treatment residues at different carbochlorination
temperatures. General spectra of the SEM-EDS
22
N. Kanari et al. / JMM 52 (1) B (2016) 17 - 24
analysis regarding to the initial sample
(DCPI+carbon) and to the carbochlorination residues
are grouped in Fig. 8.
Table 1. Identified phases in the carbochlorination residues
of DCPI at different temperatures
Temperature, °C
Initial
625
650
Ca2P2O7, CaCl2.4H2O,
CaCl2.2H2O, C
CaCl2.4H2O, CaCl2.2H2O,
Ca2P2O7, C
725
CaCl2.2H2O, CaCl2, Ca2P2O7, C
775
CaCl2.2H2O, CaCl2, C
750
As expected, the initial sample is composed of Ca,
P, O and C. The carbochlorination residue at 650°C
displays a broad peak of chlorine which can be
assigned to calcium chloride. The spectra of the
residue obtained at 700°C and especially of that
produced from 750°C are characterized by a
significant decrease of the phosphorus peak intensity
indicating its remove from the residue due to high
volatility of the phosphorus chlorides already
generated during reaction of Cl2+CO with DCPI. The
gas phase of the carbochlorination tests is cooled at
room temperature and no substantial solid condensate
is observed during treatment at T≤750°C. This
observation reinforces the hypothesis that the most
likely chlorinated compounds of phosphorus is PCl3
having a sufficient vapor pressure at room
temperature (see Fig. 4) to leave with exhausted
gases.
The results of the XRD analysis applied to the raw
sample (DCPI+carbon) and to the treatment residues
are summarized in Table 1.
Ca2P2O7, CaCl2.2H2O, C
675
700
Figure 8. SEM-EDS spectra of the (DCPI+C) initial
sample and treatment residues obtained during
carbochlorination by N2+Cl2 at different
temperatures
Main crystallized phases
identified by XRD
CaHPO4, CaHPO4.2H2O, C*
CaCl2.2H2O, Ca2P2O7, C
CaCl2.2H2O, CaCl2, C
Main phases of the raw samples are CaHPO4,
CaHPO4.2H2O and carbon. However, as mentioned in
the Section 2, CaHPO4 and CaHPO4.2H2O are
transformed into Ca2P2O7 at temperatures higher than
400°C. The presence of the CaCl2.2H2O in the
carbochlorination residue generated at 625 °C is
confirmed by XRD. One may mention that the
identification of the hydrate species for CaCl2
(CaCl2.2H2O and CaCl2.4H2O) is due to the
hygroscopic character of the CaCl2 which is
transformed into its hydrate forms during sample
preparation and XRD measurement.
Note that these hydrated species are the
predominant phases of the carbochlorination residues
at temperatures higher than 675 °C. The calcium
pyrophosphate (Ca2P2O7) phase is detected by XRD
up to 725 °C, indicating that the almost full
breakdown of the Ca2P2O7 structure is achieved
beyond this temperature. The presence of carbon in
the carbochlorination residues is also detected during
the treatment at each temperature between 625 and
775 °C. This is due to the fact that the quantity of
carbon used is about 1.5 times higher than that of
amount assumed for the carbochlorination reactions.
Further, some isothermal tests of carbon in Cl2+N2
stream between 650 and 750 °C (with a % ML less
than 1.5 %) indicated that the carbon does not react
with this chlorinating gaseous mixture.
These experimental evidences and assumptions (i.e.
the phosphorus trichloride is volatilized; calcium
chloride remained totally in the residue; carbon is
consumed only for the carbochlorination reactions)
permit using the percent mass loss for describing the
reaction extent for temperatures lower than 775 °C.
According to the data processing of Fig. 7, the
Arrhenius’ diagram is established for temperature range
625-750 °C and it is exhibited in Fig. 9. It depicts the
evolution of the apparent carbochlorination rate (on
N. Kanari et al. / JMM 52 (1) B (2016) 17 - 24
logarithm scale) as a function of the inverse of the
absolute temperature according to the kinetic equation
and models described elsewhere [24, 27]. Note that the
figures of the reaction rate deduced from % ML are
corrected due to an apparent interaction of the silica
sample boat with C+Cl2. A mean value of the apparent
activation energy of about 104 kJ/mol is calculated from
the data plotting of this Figure. Such a value tends to
indicate that the overall reaction rate of the Ca2P2O7
chlorination with Cl2+C is expected to be controlled by
the chemical reaction.
at low temperatures and by using carbon instead of
CO as a reducing agent. Carbochlorination reaction of
calcium pyrophosphate is almost fully completed at
750 °C, leading to the separation of phosphorus
chlorinated compounds from calcium chloride. A
value of the apparent activation energy of about
104 kJ/mol characterizes the carbochlorination of
Ca2P2O7 in the temperature range from 625 to
750 °C.
The developed process can be envisaged as an
alternative of the known wet and thermal methods for
the beneficiation of the low grade phosphorus ores.
Further, it can be used for the recycling and extraction
of phosphorus from various wasted materials.
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Figure 9. Arrhenius diagram for the carbochlorination of
the DCPI at 625-750 °C
4. Conclusions
The
dicalcium
phosphate
dihydrate
(CaHPO4.2H2O - brushite) is converted into calcium
pyrophosphate (Ca2P2O7) at temperatures higher than
400°C through monetite (CaHPO4) as intermediate
phase.
The thermodynamic predictions showed that the
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zone.
Kinetics of the Ca2P2O7 chlorination is enhanced
23
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